CN102794201A - Preparation method of catalyst for promoting conversion of ammonia nitrogen in coking wastewater - Google Patents
Preparation method of catalyst for promoting conversion of ammonia nitrogen in coking wastewater Download PDFInfo
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- CN102794201A CN102794201A CN2012102532348A CN201210253234A CN102794201A CN 102794201 A CN102794201 A CN 102794201A CN 2012102532348 A CN2012102532348 A CN 2012102532348A CN 201210253234 A CN201210253234 A CN 201210253234A CN 102794201 A CN102794201 A CN 102794201A
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Abstract
The invention discloses a preparation method of catalyst for promoting conversion of ammonia nitrogen in coking wastewater, which comprises the following steps: proportionally weighing copper nitrate, chromium acetate, lead sulfide and the like to prepare a mixed solution, and mixing an organic compound containing alkyl group and aryl group, a certain amount of format reagent, dry aether and the mixed solution; taking right amounts of iron chloride and sodium hydroxide, reacting to generate an iron oxide precipitate, washing, adding ketoglutaric sodium hydroxide, dissolving under the action of ultrasonic, and dropwisely adding hydrochloric acid while heating, thereby forming an iron oxide colloid; and isometrically mixing the colloid and the heavy metal organic compound, uniformly stirring, drying to obtain a catalyst precursor, carrying out step-by-step roasting, forming and grinding. Under the condition of normal pressure, the temperature of steam is utilized to directly convert ammonia gas in wastewater into nitrogen gas which is discharged into air, thereby avoiding the problem of secondary pollution; and the invention has the advantages of low cost and high ammonia nitrogen removal rate.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst that promotes that ammonia nitrogen transforms in the coking chemical waste water, bend in sewage treatment area.
Background technology
Coking chemical waste water is mainly derived from industrial water and the steam condensation waste water in the first cold-peace coking production process of coke-stove gas.Its COD concentration surpasses 4000mg/L, and ammonia nitrogen concentration surpasses 7000mg/L, exists with the form of NH3-N, and because the existence of a large amount of ammonium salts in the waste water causes the required nitrogenous source of biological cleaning superfluous, gives and handle the big difficulty of bringing up to standard.In addition, coking chemical waste water comprises a large amount of strong carcinogens, and along with industrial expansion, discharge capacity increases year by year, when environment has been caused severe contamination also direct threats to our mankind itself's health.
At present; There is multiple technology capable of using in processing to high-concentration ammonia nitrogenous wastewater; Such as " catalytic wet air oxidation method " is a kind of new technology of treatment of high concentration waste water; This method with innocuous substances such as organic matter and NH3N difference oxidation Decomposition N2 and water, reaches the purpose of purification under the condition of high temperature (0.5-2.0MPa) and catalyst (oxide, noble metal etc.) existence.In addition; The technology of utilizing the ammonia still process method to remove wastewater from chemical industry middle and high concentration ammonia nitrogen neither not have; Such as publication number is CN102351265A; Name is called in " a kind of coking production remained ammonia negative pressure ammonia distillation process and device " disclosed method and in desulfurizing tower ammonia vapour porch a Venturi tube is set in advance, and distilled ammonia wastewater/cyclic ammonia water heat exchanger and distilled ammonia wastewater circulating pump are set at the bottom of ammonia still; Open heat exchanger and circulating pump then; The heat of cyclic ammonia water is brought in the ammonia still by distilled ammonia wastewater; When the ammonia still process tower top temperature reaches 60～80 ℃, open into Venturi tube doctor solution pipeline valve, ammonia vapour is sucked desulfurizing tower; Open remained ammonia pump and distilled ammonia wastewater pump afterwards, remaining ammoniacal liquor is got into the ammonia still processing through heat exchanger get final product.
Yet, in the above prior art, be not to need hot conditions; Though under steam condition, just can transform nitrogen to ammonia exactly; But owing to contain multiple other materials in the gas that the deficiency of technology own causes discharging, product is impure and concentration is not high, has the risk that causes the secondary pollution problem.
Summary of the invention
Need when the catalysis condition of HTHP could ammonia changed into the expensive problem of nitrogen and combine the ammonia still process blow-off method to cause secondary pollution problem to air with catalyst to above prior art; Providing a kind of just can promote wastewater from chemical industry middle and high concentration ammonia nitrogen to change into the Preparation of Catalyst and the application process thereof of nitrogen in right ammonia process; The temperature that the present invention adopts mixing method to prepare can to utilize steam directly changes into the catalyst of nitrogen discharge in the atmosphere with the ammonia in the waste water; Avoided secondary pollution problem; And cost is low, and ammonia nitrogen removal frank is high.
In order to achieve the above object, the technical scheme of taking is:
A kind of method for preparing catalyst that promotes that ammonia nitrogen transforms in the coking chemical waste water is characterized in that:
(1) configuration of heavy metallic salt mixed liquor: the copper nitrate, chromic acetate, vulcanized lead, chromium chloride, vanadium chloride, strontium carbonate, zinc nitrate, titanium sulfate, cobalt chloride, the cadmium sulfide solution that take by weighing different quality according to a certain ratio;
(2) the heavy metal organic compound is synthetic: choosing the organic compound and the above-mentioned heavy metal salt solution mix that have alkyl and aromatic radical, add a certain amount of grignard reagent and dry diethyl ether, is to react 5～7 hours under 70 ℃～80 ℃ conditions in temperature;
(3) preparation of nano-titanium oxide colloid: get quality and be equivalent to a huge sum of money and bend the titanium chloride of 0.35～0.40 times of weight of organic compound and mix, add water, be heated to 50 ℃～58 ℃ all after the dissolving, use the NaOH volumetric soiutions pH=10.7 of concentration as 6M; Stir, under constant temperature, generate iron oxide precipitation, spend deionised water; Remove unnecessary salt, add total mass ratio again and be 0.06% ketoglutaric acid, drip 3～5 of the NaOH solution of 2M simultaneously; Under the ultrasonic wave condition, quicken its dissolving; Drip HCl adjustment pH=4.5 then, water-bath heating 40～60min forms needed titanium oxide colloid under 72 ℃～77 ℃ conditions;
(4) wet-mixed: press the nano-titanium oxide colloid and mix, stir, make its decentralization even with mixer with heavy metal organic compound equal-volume;
(5) oven dry: 108 ℃ of bake dryings in baking oven get catalyst precursor;
(6) segmentation roasting: be that 0.3MPa, temperature are 400 ℃ of following roastings 5 hours in negative pressure then, 450 ℃ of roastings 2.6 hours, 700 ℃ of roastings 2.0 hours, 600 ℃ of following roastings 1.8 hours, rapid cool drying under normal temperature grinds to form 0.20～0.26mm after the moulding.
A said different huge sum of money is bent salt by mass percentage:
Said alkyl compound is two or more in chloromethanes, ethane, propane, secondary butane, the uncle's butane, and compound aromatic base is two or more in p-methylphenyl, phenylalanine, nitrobenzene, diphenyl methane, the ethylbenzene.
Beneficial effect:
(1) can not cause secondary pollution directly by being reduced into nitrogen discharge to the ammonia nitrogen in the wastewater from chemical industry to environment;
(2) to the water quality situation of wastewater from chemical industry, selected with the copper nitrate to be main catalyst, with strong points.
The specific embodiment:
Taking by weighing copper nitrate, chromic acetate, vulcanized lead, chromium chloride, vanadium chloride, strontium carbonate, zinc nitrate, titanium sulfate, cobalt chloride, cadmium sulfide at first according to a certain ratio is configured to a huge sum of money and bends mixed salt solution; The organic compound that will contain alkyl and aromatic radical again mixes with above-mentioned mixed liquor; Mix with above-mentioned mixed liquor after adding a certain amount of grignard reagent and dry diethyl ether again, under 70 ℃～80 ℃ conditions, reacted 5～7 hours; Then, get quality and be equivalent to the titanium chloride that a huge sum of money is bent 0.35～0.40 times of weight of organic compound, add water, be heated to 50 ℃～58 ℃ and make its whole dissolvings; Use the NaOH volumetric soiutions of concentration again, and stir when regulating pH to 10.7, under constant temperature, generate titanium oxide and precipitate as 6M; Spend deionised water again, remove unnecessary salt, add total mass ratio afterwards and be 0.06% ketoglutaric acid; Drip 3～5 of the NaOH solution of 2M simultaneously, under the ultrasonic wave condition, quicken its dissolving again, and then drip HCl and adjust pH value to 4.5; Water-bath heating 40～60min can form needed titanium oxide colloid under 72 ℃～77 ℃ conditions.Press the nano-titanium oxide colloid again and mix, and it is uniformly dispersed with the mixer stirring with huge sum of money organic compound equal-volume in the wrong; Place 108 ℃ of baking oven oven dry can get complex catalyst precursor again; Then, be that 0.3MPa, temperature are 400 ℃ of following roastings 5 hours in negative pressure, again 450 ℃ of following roastings 2.6 hours; Again 700 ℃ of following roastings 2.0 hours; Afterwards 600 ℃ of following roastings 1.8 hours, rapid cool drying under normal temperature at last, moulding also grinds to form 0.20～0.26mm and gets final product.
Said different heavy metallic salt is by mass percentage:
Said alkyl compound is two or more in chloromethanes, ethane, propane, secondary butane, the uncle's butane, and compound aromatic base is two or more in p-methylphenyl, phenylalanine, nitrobenzene, diphenyl methane, the ethylbenzene.
Instance 1:
A said different huge sum of money is bent salt by mass percentage:
Copper nitrate 10g, chromic acetate 8g, vulcanized lead 7g,
Chromium chloride 12g, vanadium chloride 6g, strontium carbonate 11g,
Zinc nitrate 19g, titanium sulfate 15g, cobalt chloride 4g,
Cadmium sulfide 8g.
Said alkyl compound is chloromethanes, ethane, and compound aromatic base is p-methylphenyl, phenylalanine, nitrobenzene, diphenyl.
Taking by weighing copper nitrate, chromic acetate, vulcanized lead, chromium chloride, vanadium chloride, strontium carbonate, zinc nitrate, titanium sulfate, cobalt chloride, cadmium sulfide at first according to a certain ratio is configured to a huge sum of money and bends mixed salt solution; The organic compound that will contain alkyl and aromatic radical again mixes with above-mentioned mixed liquor; Mix with above-mentioned mixed liquor after adding a certain amount of grignard reagent and dry diethyl ether again, reaction is 5 hours under 70 ℃ of conditions; Then, get the titanium chloride that quality is equivalent to 0.35 times of weight of heavy metal organic compound, add water, be heated to 50 ℃ and make its whole dissolvings; Use the NaOH volumetric soiutions of concentration again, and stir when regulating pH to 10.7, under constant temperature, generate titanium oxide and precipitate as 6M; Spend deionised water again, remove unnecessary salt, add total mass ratio afterwards and be 0.06% ketoglutaric acid; Drip 3 of the NaOH solution of 2M simultaneously, under the ultrasonic wave condition, quicken its dissolving again, and then drip HCl and adjust pH value to 4.5; Water-bath heating 40min can form needed titanium oxide colloid under 72 ℃ of conditions.Press the nano-titanium oxide colloid again and mix, and it is uniformly dispersed with the mixer stirring with heavy metal organic compound equal-volume; Place 108 ℃ of baking oven oven dry can get complex catalyst precursor again; Then, be that 0.3MPa, temperature are 400 ℃ of following roastings 5 hours in negative pressure, again 450 ℃ of following roastings 2.6 hours; Again 700 ℃ of following roastings 2.0 hours; Afterwards 600 ℃ of following roastings 1.8 hours, rapid cool drying under normal temperature at last, moulding also grinds to form 0.20mm and gets final product.
Gather the waste water sample of Changzhou drugmaker; Utilize the catalyst of being processed by said method that the ammonia nitrogen in the waste water is handled then, the ammonia nitrogen concentration after handling in this waste water is reduced to 0.2mg/L from 10000mg/L, and ammonia nitrogen removal frank is 99.99%; Simultaneously, record airborne NH
3Content is 1.1mg/m
3, reach national ammonia secondary discharge standard.
Instance 2:
Copper nitrate 24g, chromic acetate 5g, vulcanized lead 5g,
Chromium chloride 11g, vanadium chloride 5g, strontium carbonate 14g,
Zinc nitrate 15g, titanium sulfate 13g, cobalt chloride 2g,
Cadmium sulfide 6g.
Said alkyl compound is propane, secondary butane, uncle's butane, and compound aromatic base is p-nitrophenyl, diphenyl methane, ethylbenzene.
Take by weighing copper nitrate, chromic acetate, vulcanized lead, chromium chloride, vanadium chloride, strontium carbonate, zinc nitrate, titanium sulfate, cobalt chloride, cadmium sulfide at first according to a certain ratio and be configured to the heavy metallic salt mixed solution; The organic compound that will contain alkyl and aromatic radical again mixes with above-mentioned mixed liquor; Mix with above-mentioned mixed liquor after adding a certain amount of grignard reagent and dry diethyl ether again, reaction is 7 hours under 80 ℃ of conditions; Then, get the titanium chloride that quality is equivalent to 0.40 times of weight of heavy metal organic compound, add water, be heated to 58 ℃ and make its whole dissolvings; Use the NaOH volumetric soiutions of concentration again, and stir when regulating pH to 10.7, under constant temperature, generate titanium oxide and precipitate as 6M; Spend deionised water again, remove unnecessary salt, add total mass ratio afterwards and be 0.06% ketoglutaric acid; Drip 5 of the NaOH solution of 2M simultaneously, under the ultrasonic wave condition, quicken its dissolving again, and then drip HCl and adjust pH value to 4.5; Water-bath heating 60min can form needed titanium oxide colloid under 77 ℃ of conditions.Press the nano-titanium oxide colloid again and mix, and it is uniformly dispersed with the mixer stirring with heavy metal organic compound equal-volume; Place 108 ℃ of baking oven oven dry can get complex catalyst precursor again; Then, be that 0.3MPa, temperature are 400 ℃ of following roastings 5 hours in negative pressure, again 450 ℃ of following roastings 2.6 hours; Again 700 ℃ of following roastings 2.0 hours; Afterwards 600 ℃ of following roastings 1.8 hours, rapid cool drying under normal temperature at last, moulding also grinds to form 0.26mm and gets final product.
Gather the waste water sample of Wuxi pharmaceutical factory; Utilize the catalyst of being processed by said method that the ammonia nitrogen in the waste water is handled then, the ammonia nitrogen concentration after handling in this waste water is reduced to 0.2mg/L from 9000mg/L, and ammonia nitrogen removal frank is 99.98%; Simultaneously, record airborne NH
3Content is 1.0mg/m
3, reach national ammonia first discharge standard.
Instance 3:
Said different heavy metallic salt is by mass percentage:
Copper nitrate 23g, chromic acetate 7g, vulcanized lead 6g,
Chromium chloride 11g, vanadium chloride 6g, strontium carbonate 7g,
Zinc nitrate 16g, titanium sulfate 14g, cobalt chloride 3g,
Cadmium sulfide 7g.
Said alkyl compound is propane, secondary butane, uncle's butane, and compound aromatic base is p-methylphenyl, nitrobenzene, diphenyl methane.
Take by weighing copper nitrate, chromic acetate, vulcanized lead, chromium chloride, vanadium chloride, strontium carbonate, zinc nitrate, titanium sulfate, cobalt chloride, cadmium sulfide at first according to a certain ratio and be configured to the heavy metallic salt mixed solution; The organic compound that will contain alkyl and aromatic radical again mixes with above-mentioned mixed liquor; Mix with above-mentioned mixed liquor after adding a certain amount of grignard reagent and dry diethyl ether again, reaction is 6 hours under 75 ℃ of conditions; Then, get the titanium chloride that quality is equivalent to 0.38 times of weight of heavy metal organic compound, add water, be heated to 55 ℃ and make its whole dissolvings; Use the NaOH volumetric soiutions of concentration again, and stir when regulating pH to 10.7, under constant temperature, generate titanium oxide and precipitate as 6M; Spend deionised water again, remove unnecessary salt, add total mass ratio afterwards and be 0.06% ketoglutaric acid; Drip 4 of the NaOH solution of 2M simultaneously, under the ultrasonic wave condition, quicken its dissolving again, and then drip HCl and adjust pH value to 4.5; Water-bath heating 50min can form needed titanium oxide colloid under 75 ℃ of conditions.Press the nano-titanium oxide colloid again and mix, and it is uniformly dispersed with the mixer stirring with heavy metal organic compound equal-volume; Place 108 ℃ of baking oven oven dry can get complex catalyst precursor again; Then, be that 0.3MPa, temperature are 400 ℃ of following roastings 5 hours in negative pressure, again 450 ℃ of following roastings 2.6 hours; Again 700 ℃ of following roastings 2.0 hours; Afterwards 600 ℃ of following roastings 1.8 hours, rapid cool drying under normal temperature at last, moulding also grinds to form 0.24mm and gets final product.
Gather the waste water sample of Shanghai pharmaceutical factory; Utilize the catalyst of being processed by said method that the ammonia nitrogen in the waste water is handled then, the ammonia nitrogen concentration after handling in this waste water is reduced to 0.25mg/L from 15000mg/L, and ammonia nitrogen removal frank is 99.98%; Simultaneously, record airborne NH
3Content is 1.0mg/m
3, reach national ammonia first discharge standard.
Claims (3)
1. method for preparing catalyst that promotes that ammonia nitrogen in the coking chemical waste water transforms is characterized in that:
(1) configuration of heavy metallic salt mixed liquor: the copper nitrate, chromic acetate, vulcanized lead, chromium chloride, vanadium chloride, strontium carbonate, zinc nitrate, titanium sulfate, cobalt chloride, the cadmium sulfide solution that take by weighing different quality according to a certain ratio;
(2) the heavy metal organic compound is synthetic: choosing the organic compound and the above-mentioned heavy metal salt solution mix that have alkyl and aromatic radical, add a certain amount of grignard reagent and dry diethyl ether, is to react 5～7 hours under 70 ℃～80 ℃ conditions in temperature;
(3) preparation of nano-titanium oxide colloid: get the titanium chloride that quality is equivalent to 0.35～0.40 times of weight of heavy metal organic compound and mix, add water, be heated to 50 ℃～58 ℃ all after the dissolving, use the NaOH volumetric soiutions pH=10.7 of concentration as 6M; Stir, under constant temperature, generate iron oxide precipitation, spend deionised water; Remove unnecessary salt, add total mass ratio again and be 0.06% ketoglutaric acid, drip 3～5 of the NaOH solution of 2M simultaneously; Under the ultrasonic wave condition, quicken its dissolving; Drip HCl adjustment pH=4.5 then, water-bath heating 40～60min forms needed colloid of iron oxide under 72 ℃～77 ℃ conditions;
(4) wet-mixed: press the nano-sized iron oxide colloid and mix, stir, make its decentralization even with mixer with heavy metal organic compound equal-volume;
(5) oven dry: 108 ℃ of bake dryings in baking oven get catalyst precursor;
(6) segmentation roasting: be that 0.3MPa, temperature are 400 ℃ of following roastings 5 hours in negative pressure then, 450 ℃ of roastings 2.6 hours, 700 ℃ of roastings 2.0 hours, 600 ℃ of following roastings 1.8 hours, rapid cool drying under normal temperature grinds to form 0.20～0.26mm after the moulding.
2. according to the said a kind of Preparation of catalysts method that promotes that ammonia nitrogen in the coking chemical waste water transforms of claim 1, it is characterized in that: said different heavy metallic salts by mass percentage:
3. according to the said a kind of method for preparing catalyst that promotes that ammonia nitrogen transforms in the coking chemical waste water of claim 1; It is characterized in that: said alkyl compound is two or more in chloromethanes, ethane, propane, secondary butane, the uncle's butane, and compound aromatic base is two or more in p-methylphenyl, phenylalanine, nitrobenzene, diphenyl methane, the ethylbenzene.
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Cited By (2)
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| CN104907047A (en) * | 2015-05-25 | 2015-09-16 | 常州大学 | Method used for treating highly concentrated ammonia-nitrogen in rare earth waste water |
| CN104907046A (en) * | 2015-05-25 | 2015-09-16 | 常州大学 | Method used for treating highly concentrated ammonia-nitrogen in circuit board etching waste water |
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| CN104907046A (en) * | 2015-05-25 | 2015-09-16 | 常州大学 | Method used for treating highly concentrated ammonia-nitrogen in circuit board etching waste water |
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